Computational and Experimental Study of Nonlinear Optical Susceptibilities of Composite Materials Based on PVK Polymer Matrix and Benzonitrile Derivatives

Theoretical and experimental investigations of the linear and nonlinear optical properties of composite materials based on the (Z)-4-(1-cyano-2-(5-methylfuran-2-yl)vinyl)benzonitrile molecule named as A, the (Z)-4-(2-(benzofuran-2-yl)-1-cyanovinyl)benzonitrile named as B and the (Z)-4-(2-(4-(9H-carbazol-9-yl)phenyl)-1-cyanovinyl)benzonitrile molecule named as C embedded into poly(1-vinylcarbazole) (PVK) polymer matrix were performed. The electronic and optical properties of A, B, and C molecules in a vacuum and PVK were calculated. The guest–host polymer structures for A, B, and C molecules in PVK were modeled using molecular dynamics simulations. The spatial distribution of chromophores in the polymer matrix was investigated using the intermolecular radial distribution (RDF) function. The reorientation of A, B, and C molecules under the influence of the external electric field was investigated by measuring the time-dependent arrangement of the angle between the dipole moment of the chromophore and the external electric field. The polarizabilities and hyperpolarizabilities of tested compounds have been calculated applying the DFT/B3LYP functional. The second- and third-order nonlinear optical properties of the molecule/PVK thin film guest–host systems were investigated by the Maker fringes technique in the picosecond regime at the fundamental wavelength of 1064 nm. The experimental results were confirmed and explained with theoretical simulations and were found to be in good agreement. The modeling of the composites in volumetric and thin-film form explains the poling phenomena caused by the external electric field occurring with the confinement effect.